JPH08151552A - Hard coat film - Google Patents

Abstract

PURPOSE: To obtain the subject film comprising an organosiloxane, a diorganosilane hydrolysate, a silyl group-containing vinylic resin, a metal chelate compound and fine particles in specific amounts, respectively, and excellent in appearance, surface hardness, etc. CONSTITUTION: This film is produced by coating a composition on a substrate film. The composition comprises (A) 100 pts.wt. (converted to an organosiloxane) of the hydrolysate of the organosiloxane of formula: R<1> Si(OR<2> )3 (R<1> is 18C organic group; R<2> is H, 1-5C alkyl, etc.,) and/or its partial condensation product, (B) 0-150 pts.wt. (converted to a diorganosilane) of the diorganosilane of formula: R<1> 1 Si(OR<2> )2 , and/or its partial condensation product, (C) 2-300 pts.wt. of a silyl group-containing vinylic resin having Si atoms bound to hydrolyzable groups and/or hydroxyl groups, (D) 0.01-50 pts.wt. of a metal chelate compound such as tri-n-butoxy(ethylacetoacetato) zirconium, and (E) fine particles having a particle diameter of 5nm to 100μm in an amount of 5-200 pts.wt. per 100 pts.wt. of the total amount of the other components.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hard coat film, and more particularly to a hard coat film, which is coated on a plastic material or the like, particularly a polyester base material, and has an appearance, a surface hardness, a scratch resistance, an adhesion property and a bending process. The present invention relates to a hard coat film that has good properties and stain resistance, is dried in a short time, and can control transparency in a wide range. The hard coat film of the present invention can be used as an abrasion resistant film, an anti-slip coat, a polishing film, an anti-glare coat film, a wallpaper for building interior and the like.

[0002]

2. Description of the Related Art In recent years, plastic substrates have good paintability, can be dried in a short time, and can control transparency in a wide range, and have a good appearance, surface hardness, scratch resistance, and adhesion. There is a demand for a hard coat film having excellent bending workability. As a coating composition satisfying some of such requirements, for example, JP-A-60-13546.
JP-A-5-34587, which discloses a composition comprising alkyltrihydroxysilane and a partial condensate thereof, colloidal silica, and a silicon-modified acrylic resin.
In Japanese Patent Publication No. 7, there is proposed a composition comprising an organotrialkoxysilane hydrolyzed condensate, a metal selected from zirconium, aluminum and titanium, a chelate compound, and a silicon-modified acrylic resin.

[0003]

However, in the above-mentioned composition of the prior art, the coating property with respect to the plastic substrate is good, the composition can be dried in a short time, the transparency in a wide range can be controlled, and the appearance can be improved. However, a hard coat film having excellent surface hardness, scratch resistance, adhesion, and bending workability has not been obtained yet. For example, JP-A-60-1354
In Japanese Patent Laid-Open No. 65-65, when a hard coat film is obtained, as shown in an example of a polycarbonate resin,
There is a problem that drying at 100 to 120 ° C. for a long time of 1 to 2 hours is required, and drying in a short time is difficult, and in JP-A-5-345877, sufficient hardness cannot be obtained. There's a problem.

The present invention has been made against the background of the above-mentioned conventional technical problems.
A hard coat film that has good coatability, can be dried in a short time, and can control transparency in a wide range, and has excellent appearance, surface hardness, scratch resistance, adhesion, bending workability, and stain resistance. The purpose is to provide.

[0005]

The present invention provides (a) a general formula R ¹ Si (OR ² ) ₃ (wherein R ¹ is an organic group having 1 to 8 carbon atoms, R ² is a hydrogen atom or a carbon number). A hydrolyzate of an organosilane represented by an alkyl group having 1 to 5 or an acyl group having 1 to 4 carbon atoms (hereinafter also referred to as "(a ') organosilane" or "(a') component"); / Or a partial condensate thereof (hereinafter also referred to as "(a) component") per 100 parts by weight in terms of organosilane, (b) the general formula R ¹ ₂ Si (OR ² ) ₂ (in the formula, R ¹ and R ² is the same as above), a hydrolyzate of diorganosilane (hereinafter also referred to as “(b ′) diorganosilane” or “(b ′) component”) and / or its partial condensate (hereinafter “( (also referred to as “b) component”) in an amount of 0 to 150 parts by weight in terms of diorganosilane, (c ) A silyl group-containing vinyl resin having at least one silyl group having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group at the end or side chain in one molecule of the polymer (hereinafter referred to as “(c) silyl group-containing vinyl”). 2 to 300 parts by weight, (d) the general formula Zr (OR ³ ) _p
(R ⁴ COCHCOR ⁵ ) _4-p , Ti (OR ³ ) _q (R
⁴ COCHCOR ⁵ ) _4-q and Al (OR ³ ) _r (R
⁴ COCHCOR ⁵ ) _3-r (In the formula, R ³ and R ⁴ are the same or different and are an alkyl group having 1 to 6 carbon atoms, R ⁵ is an alkyl group having 1 to ⁵ carbon atoms or an alkoxy group having 1 to 16 carbon atoms. , P and q are integers of 0 to 3 and r is an integer of 0 to 2), at least one metal chelate compound selected from the group of compounds represented by the following (hereinafter referred to as “(d) metal chelate compound” or "(D) component") is 0.01
˜50 parts by weight, and (e) particle size 5 nm to 100 μ
The fine particles of m (hereinafter, also referred to as “(e) fine particles” or “(e) component”) are 100 in total of the components (a) to (d).
It is intended to provide a hard coat film obtained by coating a substrate with a composition containing 5 to 200 parts by weight based on parts by weight (solid content conversion).

First, the composition used for the hard coat film of the present invention will be described in detail according to the constitutional requirements. Component (a): Component (a) has the general formula R ¹ Si (OR ² ).
It is a hydrolyzate and / or a partial condensate obtained by hydrolyzing and condensing (a ') organosilane represented by ₃ and functions as a binder in the composition used in the present invention. It is a thing. R ¹ in the organosilane (a ′) is an organic group having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a butyl group, a pentyl group, a hexyl group, In addition to chain, branched or cyclic alkyl groups such as cyclohexyl group, heptyl group and octyl group, γ-chloropropyl group, vinyl group, 3,3,3-trifluoropropyl group, γ-glycidoxypropyl group , Γ-mercaptopropyl group, γ
And functional alkyl groups such as methacryloxypropyl group, phenyl group, xylyl group, and 3,4-epoxycyclohexylethyl group, and aryl groups. When the carbon number of R ¹ exceeds 8, the hydrolysis rate, the drying property of the coating film, and the hardness may decrease, which is not preferable. R ² in the organosilane (a ′) is a hydrogen atom or has 1 to 1 carbon atoms.
An alkyl group having 5 or an acyl group having 1 to 4 carbon atoms,
For example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, tert-
Examples thereof include a butyl group and an acetyl group. When the carbon number of R ² exceeds 5, the hydrolysis rate, the drying property of the coating film,
The hardness may decrease, which is not preferable.

Specific examples of these (a ') organosilanes include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, and n-propyltrimethoxysilane.
Propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3,3,3 -Trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane,
γ-mercaptopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane,
Examples thereof include 3,4-epoxycyclohexylethyltrimethoxysilane and 3,4-epoxycyclohexylethyltriethoxysilane, with methyltrimethoxysilane and methyltriethoxysilane being preferred.

These (a ') organosilanes may be used alone or in combination of two or more. Further, among the above-mentioned (a ′) organosilane,
It is preferable that 80 mol% or more is CH ₃ Si (OR ² ) ₃ . The weight average molecular weight of the component (a) is preferably 800 to 100,000, more preferably 1,000 to 50,000.

Component (b): Component (b) has the general formula R ¹ ₂
Si (OR ² ) ₂ [In the formula, R ¹ and R ² are the above (a).
The same as R ¹ and R ² used in the organosilane used as the component] (b ′) a hydrolyzate and / or partial condensate obtained by hydrolyzing and condensing the diorganosilane. In the composition used in the present invention, it functions as a binder and softens the coating film to improve the bending workability of the coating film. R ¹ and R ² of such (b ') in diorganosilane are the same as R ¹ and R ² of the organosilane.

Specific examples of these (b ') diorganosilanes include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane and di-n.
-Propyldiethoxysilane, di-i-propyldimethoxysilane, di-i-propyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane and the like can be mentioned, but dimethyldimethoxysilane and dimethyldiethoxysilane are preferable. is there. These (b ') diorganosilanes may be used alone or in combination of two or more. The component (b) is used as a cocondensate with the component (a), and the weight average molecular weight of the cocondensate is preferably 800 to 100,
000, more preferably 1,000 to 50,000. The ratio of the component (b) in the composition of the present invention is
0 to 150 parts by weight, preferably 5 to 10 parts by weight of (b ') diorganosilane per 100 parts by weight of component (a').
0 parts by weight, more preferably 10 to 60 parts by weight,
If it exceeds 150 parts by weight, the hardness and stain resistance of the obtained film will be reduced.

(C) Silyl group-containing vinyl resin; (c)
The silyl group-containing vinyl resin is a vinyl polymer having a carbon skeleton as a main chain, and has a silyl group having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group at the terminal or side chain in one molecule of the polymer. At least 1, preferably 2
More than one, most of the silyl groups are represented by the following general formula (In the formula, R ^{1 and} R ² are the same as described above, and n represents a positive integer of 1 to 3).

The silyl group-containing vinyl resin (c) is, for example, represented by the following general formula: (In the formula, R ^{1 and} R ² are the same as those described above, and X represents a monovalent organic group having 2 to 10 carbon atoms and containing a radically polymerizable double bond). It can be produced by copolymerizing "a radically polymerizable silane compound") with various vinyl compounds. Examples of such an organic group X include vinyl, 2-propenyl, 3-acryloxypropyl, 3-methacryloxypropyl, 4-vinylphenyl, 2- (4-vinyl) phenylethyl and the like.

As such various vinyl compounds,
As long as an adduct with the radically polymerizable silane compound can be obtained, it is not particularly limited, and examples include (meth)
(Meth) acrylic acid alkyl esters such as methyl acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate; (meth) acrylic acid, itaconic acid, fumaric acid, etc. Unsaturated carboxylic acids; and acid anhydrides such as maleic anhydride; epoxy compounds such as glycidyl (meth) acrylate; amino compounds such as dimethylaminoethyl (meth) acrylate and aminoethyl vinyl ether; (meth) acrylamide, crotonamide, Amide compounds such as itaconic acid amide and maleic acid amide; and one or more kinds selected from acrylonitrile, methacrylonitrile, styrene, α-methylstyrene, vinyl chloride, vinyl acetate, vinyl propionate, and the like. The silyl group-containing vinyl resin (c) can be obtained by copolymerizing the vinyl compound and the radical-polymerizable silane compound by a known method in the presence of a radical-generating compound.

Preferred examples of these vinyl compounds are (meth) acrylic acid alkyl esters, more preferably methacrylic acid alkyl esters, particularly preferably methyl methacrylate, ethyl methacrylate and butyl methacrylate. , Cyclohexyl methacrylate can be mentioned. The ratio of the radically polymerizable silane compound in the silyl group-containing vinyl resin (c) thus produced is usually in terms of silicon element,
0.01 to 20% by weight, preferably 0.1 to 10% by weight
If it is less than 0.01% by weight, the effect of improving weather resistance and adhesion is low, while if it exceeds 20% by weight, the storage stability of the composition may be lowered.

The molecular weight of the (c) silyl group-containing vinyl resin is usually 5,0 as determined by gel permeation chromatography (GPC).
00-100,000, preferably 10,000-5
It is 10,000. Those having a weight average molecular weight of less than 5,000 or more than 100,000 are not preferable because the viscosity may be too low or the viscosity may be too high and the coating workability may be deteriorated. Further, the (c) silyl group-containing vinyl resin has a glass transition temperature determined by a differential thermal analysis method of usually -60 ° C to + 150 ° C, and a coating film hardness of less than -60 ° C cannot be obtained. Sometimes, while 15
If it exceeds 0 ° C, the film formability may decrease.

The proportion of the silyl group-containing vinyl resin (c) in the composition is 2 to 300 parts by weight, preferably 50 to 100 parts by weight relative to 100 parts by weight of the (a ') organosilane which is the raw material of the component (a). 200 parts by weight, more preferably 80 to 15
If the amount is 0 parts by weight and the amount is less than 2 parts by weight, the bending adhesion of the obtained film may be low, while if it exceeds 300 parts by weight, the weather resistance and stain resistance of the obtained coating film may be deteriorated. The above (c) silyl group-containing vinyl resins can be used alone or in combination of two or more.

(D) Metal chelate compound: The (d) metal chelate compound of the present invention has the general formula Zr (OR ³ ) _p
(R ⁴ COCHCOR ⁵ ) _4-p , Ti (OR ³ ) _q (R
⁴ COCHCOR ⁵ ) _4-q and Al (OR ³ ) _r (R
⁴ COCHCOR ⁵ ) _3-r , which is at least one selected from the group of compounds, and which promotes the condensation reaction between the above components (a) and (b) and (c) the silyl group-containing vinyl resin. , (A) and (b) and the component (c) are considered to form a copolymer.

(D) R ³ and R ⁴ in the metal chelate compound are the same or different and each is an alkyl group having 1 to 6 carbon atoms,
Specifically, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group,
Examples include n-pentyl group and phenyl group. Also, R
⁵ is an alkyl group having 1 to 5 carbon atoms, as well as 1 to 1 carbon atoms
6 is an alkoxy group, and examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, sec-butoxy group, t-
Examples thereof include butoxy group, lauryloxy group and stearoxy group. In addition, pq in the metal chelate compound (d) is 0 to
The integer of 3 and r show the integer of 0-2.

Specific examples of these (d) metal chelate compounds include tri-n-butoxy (ethylacetoacetate) zirconium, di-n-butoxy-bis (ethylacetoacetate) zirconium and n-butoxy-tris (ethyl). Acetoacetate) zirconium, tetrakis (n-propylacetoacetate) zirconium, tetrakis (acetylacetoacetate) zirconium,
Zirconium chelate compounds such as tetrakis (ethylacetoacetate) zirconium; diisopropoxy-
Titanium chelate compounds such as bis (ethylacetoacetate) titanium, diisopropoxy-bis (acetylacetate) titanium, diisopropoxy-bis (acetylacetate) titanium; diisopropoxy (ethylacetoacetate) aluminum, diisopropoxy (acetyl) Acetonate) aluminum, isopropoxy-bis (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum,
Tris (acetylacetonate) aluminum, monoacetylacetonate-bis (ethylacetoacetate)
Examples thereof include aluminum chelate compounds such as aluminum. Preferred among these (d) metal chelate compounds are tri-n-butoxy (ethylacetoacetate) zirconium, diisopropoxy-bis (acetylacetonato) titanium, diisopropoxy (ethylacetoacetate) aluminum, tris ( Ethyl acetoacetate) aluminum. These (d) metal chelate compounds may be used alone or in combination of two or more. Further, as the component (d), a partial hydrolyzate of these metal chelate compounds can also be used.

The proportion of the metal chelate compound (d) in the composition is 0.01 to 50 parts by weight, preferably 0.1 to 100 parts by weight of the organosilane (a ') which is the raw material of the component (a). -50 parts by weight, more preferably 0.5-10
If it is less than 0.01 parts by weight, (a)-
The copolymer of the component (b) and the component (c) was insufficiently formed, and the hardness of the hard coat film was decreased, while
If it exceeds the weight part, the bending adhesion of the hard coat film is deteriorated, which is not preferable.

(E) Fine Particles The fine particles (e) of the present invention have a particle diameter of 5 nm to 100 μm.
m, preferably 10 nm to 1 μm, more preferably 1
It is from 0 to 100 nm, and in the composition of the present invention, it functions to strengthen the hardness of the surface of the hard coat film and improve wear resistance. It is difficult to produce fine particles having a particle diameter of less than 5 nm, while if it exceeds 100 μm, the appearance of the surface of the coated body may be deteriorated and particles may be precipitated during storage, which is not preferable.

(E) The composition of the fine particles includes metal particles such as iron, copper, nickel, stainless steel and silicon; metal nitrides such as silicon nitride, boron nitride and titanium nitride, silicon oxide, aluminum oxide, titanium oxide and oxide. Examples thereof include metal oxides such as zirconium, cerium oxide, zinc oxide, antimony oxide, boron oxide, tin oxide, and iron oxide; metal carbides such as tungsten carbide, molybdenum carbide, and silicon carbide; carbon allotropes such as graphite and diamond. .

Preferred examples of the composition of these fine particles include metal nitrides, metal oxides, more preferably metal oxides, and among these, silicon oxide can be mentioned as a preferable example. The fine particles (e) can be used alone or in combination of two or more. Further, the fine particles (e) have the following shapes:
It may have a spherical shape, a needle shape, a plate shape, or an irregular shape. The fine particles (e) of the present invention can be used as a powder or a dispersion liquid, but a dispersion liquid is preferable from the viewpoint of easy uniform dispersion. As a dispersion medium for such fine particles (e), water or an organic solvent such as methanol, isopropanol, n-butanol, ethyl cellosolve, methyl isobutyl ketone, toluene, xylene and dimethylacetamide can be used.

(E) Specific examples of the fine particles include metal oxides such as Admafine [Tatsumori Co., Ltd., spherical silicon oxide], Aerosil 130, 200, and 300 [Japan Aerosil Co., Ltd., ultrafine particles. Anhydrous silica], SG flakes (manufactured by Nippon Sheet Glass Co., Ltd., ultrafine glass flakes), Teismo [Otsuka Chemical Co., Ltd., potassium titanate whiskers], and as silicon carbide, Showa Denko KK
Manufactured by Ube Industries, Ltd., silicon nitride SN-E-10, and the like can be given as examples of manufactured products, ultra densics, and metal nitrides. Among these, colloidal silica dispersed in an organic solvent is preferable as the dispersion liquid of the metal oxide because it can be easily dispersed in the composition.

As the organic solvent-dispersed colloidal silica,
For example, Nissan Chemical Industry Co., Ltd., isopropanol silica sol (IPA-ST), methanol silica sol (MA-
ST-M), butanol silica sol (NBA-ST),
Examples thereof include ethyl cellosolve silica sol (ETC-ST), methyl isobutyl ketone silica sol (MIBK-ST); manufactured by Catalysts & Chemicals Industry Co., Ltd., Oscal, and the like, and particularly preferably alcohol-based solvent-dispersed colloidal silica.

(E) The ratio of the fine particles in the composition is (a)
To 5 to 200 relative to 100 parts by weight of the solid content of the component (d).
Parts by weight, preferably 20 to 150 parts by weight, more preferably 50 to 120 parts by weight. If the amount is less than 5 parts by weight, the surface hardness of the hard coat film is not sufficient, while 20
If it exceeds 0 parts by weight, stain resistance and bending adhesion are poor.

The composition used in the present invention may contain β-diketones and / or β-ketoesters represented by the general formula R ⁴ COCH ₂ COR ⁵ as a stabilizer. That is, by coordinating with the metal atom in the (d) metal chelate compound (zirconium, titanium and / or aluminum compound) present in the composition containing the components (a) to (e) as the main components, (A)-(b) depending on the metal chelate compound of
It is considered that the action of promoting the condensation reaction of the component and / or the component (c) is suppressed, and the action of improving the storage stability of the obtained composition is performed. β-diketones and /
Or R ⁴ and R constituting β-ketoesters
⁵ is the same as R ⁴ and R ⁵ constituting the metal chelate compound (d).

Specific examples of the β-diketones and / or β-ketoesters include acetylacetone, methyl acetoacetate, ethyl acetoacetate, and acetoacetic acid-n-.
Propyl, acetoacetic acid-i-propyl, acetoacetic acid-n
-Butyl, acetoacetic acid-sec-butyl, acetoacetic acid-
t-butyl, 2,4-hexane-dione, 2,4-heptane-dione, 3,5-heptane-dione, 2,4-octane-dione, 2,4-nonane-dione, 5-methyl-hexane- Zion etc. can be mentioned. Of these, ethyl acetoacetate and acetylacetone are preferable, and acetylacetone is particularly preferable. These β-diketones and / or β-ketoesters may be used alone or in combination of two or more.
The amount of the β-diketones and / or β-ketoesters is 2 mol or more, preferably 3 to 20 mol, per 1 mol of the (d) metal chelate compound, and if less than 2 mol, storage stability of the obtained composition will be improved. Will be inferior.

In the composition used in the present invention, the components are uniformly mixed to adjust the solid content and viscosity, and an organic solvent is added for the purpose of improving the drying rate and storage stability during coating. This organic solvent can be selected from among organic materials having a property of volatilizing and evaporating after being dried and cured. The water content of this organic solvent is required to be as low as possible for the purpose of ensuring the storage stability of the composition, and is usually 0.15% by weight or less, preferably 0.05% by weight or less, and particularly preferably. Is an organic solvent having a water content of 0.01% by weight or less.
The organic solvent is not particularly limited as long as it can uniformly mix the components (a) to (e), and for example, alcohols, aromatic hydrocarbons, ethers, ketones,
Esters and the like are preferable.

Of these, examples of alcohols include monohydric alcohols and dihydric alcohols, and among these, the monohydric alcohols are preferably saturated aliphatic alcohols having 1 to 8 carbon atoms. Specific examples of these alcohols include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol. Examples thereof include monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether and the like.

Specific examples of aromatic hydrocarbons include benzene, toluene, xylene and the like, and specific examples of ethers include dimethoxymethane, tetrahydrofuran, dioxane, ethylene glycol monoethyl ether acetate, and other ketones. As a specific example, acetone,
Methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone and the like can be mentioned, and specific examples of the esters include ethyl acetate, propyl acetate, butyl acetate, propylene carbonate, γ-butyrolactone and the like. These organic solvents may be used alone or in combination of two or more. The organic solvent used in the present invention is (a ') organosilane, (b') alcohol produced as a by-product of hydrolysis of diorganosilane, or (e) an organic dispersion medium of fine particles as an organic solvent. It can also be used. Further, the ratio of the organic solvent in the composition is not particularly limited, and an amount that adjusts the total solid content concentration according to the purpose of use is used.

Further, the composition of the present invention usually comprises (a)
~ Hydrolysis / condensation of (a ') organosilane constituting component (a) and / or (b') diorganosilane constituting component (b) when a composition containing component (e) is prepared Water is added for use. Examples of the water used here include distilled water and ion-exchanged water. The amount of water used is usually 1.2 to 3.0 mol, preferably 1.3 to 2.0 mol, and 1 mol of (b ') diorganosilane to 1 mol of (a') organosilane. On the other hand, it is usually 0.8 to 2.0 mol, preferably 0.9 to 1.5 mol.

Further, in order to cure the composition of the present invention more quickly, a curing accelerator may be used,
In order to cure at a relatively low temperature, it is more effective to use a curing accelerator together.

As such a curing accelerator, among inorganic or organic compounds having an effect of accelerating the hydrolysis of alkoxysilane (organosilane and / or diorganosilane) contained in the composition and the condensation reaction of silanols. One or more can be selected from the above, and specific examples thereof include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, inorganic and organic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid and toluenesulfonic acid. Quaternary ammonium hydroxide such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide; ammonia, triethylamine, tributylamine, morpholine, pyridine, piperidine, ethylenediamine, diethylenetriamine, ethanol Amine, diethanolamine, amines such as triethanolamine; 3-aminopropyltriethoxysilane, N (2-aminoethyl) -3-aminosilanes such as aminopropyltrimethoxysilane; and

(C ₄ H ₉ ) ₂ Sn (OCOC ₁₁ H ₂₃ ) ₂ ,
_{(C 4 H 9) 2 Sn} (OCOCH = CHCOOCH 3) 2,
_{(C 4 H 9) 2 Sn} (OCOCH = CHCOOC 4 H 9)
_{2, (C 8 H 17)} 2 Sn (OCOC 11 H 23) 2, (C 8 H
₁₇ ) ₂ Sn (OCOCH = CHCOOCH ₃ ) ₂ , (C ₈ H
₁₇ ) ₂ Sn (OCOCH = CHCOOC ₄ H ₉ ) ₂ , (C _{8
H 17) 2 Sn (OCOCH =} CHCOOC 8 H 17) 2, Sn
(OCOCC ₈ H ₁₇ ) ₂ , (C ₄ H ₉ ) ₂ Sn (SCH
₂ COO), (C ₄ H ₉ ) ₂ Sn (SCH ₂ COOC _{8
H 17) 2, (C 8} H 17) 2 Sn (SCH 2 COO),
_{(C 8 H 17) 2 Sn} (SCH 2 CH 2 COO), (C 8
_{H 17) 2 Sn (SCH 2} COOCH 2 CH 2 CH 2 OC
OCH ₂ S), (C ₈ H ₁₇ ) ₂ Sn (SCH ₂ CH ₂ CO
_{OC 8 H 17) 2, (} C 8 H 17) 2 Sn (SCH 2 CH 2 CO
OC ₁₂ H ₂₅ ) ₂ ,

[0036] (C ₄ H ₉ ) ₂ Sn = S, (C ₈ H ₁₇ ) ₂ Sn = S,

(C ₈ H ₁₇ ) Sn (OCOC ₁₁ H ₂₃ ) ₃ ,
(C ₈ H ₁₇ ) Sn (SCH ₂ CH ₂ COOC
_{8 H 17) 3, (C} 8 H 17) Sn (SCH 2 CH 2 COO
Organotin compounds such as C ₁₂ H ₂₅ ) ₃ , and (C
_{4 H 9) 2 Sn = O} , C 4 H 9 SnO, (C 8 H 17) 2 S
n = O, an organic tin oxide such as C ₈ H ₁₇ SnO, a silicon alkoxide such as tetraethoxysilane, ethyl silicate-40 [manufactured by Tama Chemical Co., Ltd.], and a reaction product of a condensation reaction product thereof, and the above organic tin oxide. Organotin compounds such as reaction products of dimethyl maleate, diethyl maleate, dioctyl phthalate, and other ester compounds can be used.

In the metal chelate compound (d) used in the present invention as a curing accelerator, a zirconium compound, a titanium compound and / or an aluminum compound in which p and q are 0 to 4 and r is 0 or 3 are used. Can also be used. Preferred examples of the curing accelerator are organic tin compounds and zirconium compounds. The ratio of these curing accelerators in the composition is usually 1 with respect to 100 parts by weight of the solid content of the composition of the present invention.
5 parts by weight or less, preferably 10 parts by weight or less are used, and 1
Addition of more than 5 parts by weight usually increases the thickening rate and gelling rate of the composition and shortens the pot life, which is not preferable.

The composition used in the present invention contains a thickener for the purpose of controlling the viscosity mainly for controlling the film thickness of the coating film, controlling the transparency of the coating film, and controlling the dispersibility of fine particles. Can be added for use. Examples of the thickener include celluloses such as hydroxypropyl cellulose, hydroxypropylmethyl cellulose and ethyl cellulose, polar vinyl polymers such as polyvinylpyrrolidone and polyvinyl acetate, and thickeners such as organic esters. Among these, preferred are celluloses. Further, specific examples of these thickeners include hydroxypropyl cellulose manufactured by Shin-Etsu Chemical Co., Ltd.,
Examples thereof include ethyl cellulose, Metrose, Poval, Troy Chemical Co., and TROYTHIX A.

The amount of the thickening agent added is from (a) to
Based on the total weight of the composition comprising the component (e),
It is 0.05 to 10% by weight, preferably 0.1 to 5% by weight. If it is less than 0.05% by weight, the effect of addition is unclear, while if it exceeds 10% by weight, dissolution of the thickener tends to be long. It is not preferable because it takes time and the undissolved thickener may precipitate. The viscosity of the coating composition to which these thickeners are added is usually 5 to 1,000 mPa · s, preferably 20 by a Brookfield type rotational viscometer.
The viscosity at the Zahn cup viscosity (cup No. 3), which is often used as a method for evaluating the viscosity of a coating liquid, is usually 8 to 120 seconds, preferably 15 to 60 seconds. Used. 5m in rotational viscosity
When the Pa · s and Zahn cup viscosity are less than 8 seconds, the addition of the thickener has no substantial effect, while the rotational viscosity is 100
When the viscosity is 0 mPa · s and the Zahn cup viscosity exceeds 120 seconds, workability is deteriorated, which is not preferable.

In addition to the composition of the present invention, a dehydrating agent such as methyl orthoformate, methyl orthoacetate and cyclohexanone dimethyl ketal, and various surfactants may be added for the purpose of further enhancing the wettability to the substrate. Further, an organically modified silicon compound called a silane coupling agent such as aminopropyltriethoxysilane, glycidoxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, or titanium coupling for the purpose of further improving the adhesion to the substrate. Agents and the like may be added.

In preparing the composition of the present invention, for example, first, a composition containing the above-mentioned components (a) to (d) is prepared, and the component (e) is added thereto, or (a), After preparing a composition comprising the components (b) and (e),
It can be prepared by a method of adding and preparing the components (c) and (d), and preferably the following preparation methods can be mentioned.

Organosilane constituting the component (a),
In a solution comprising diorganosilane (b) constituting the component, (c) silyl group-containing vinyl-based resin, and (d) metal chelate compound, 1.2 to 3 mol of water and diorgano relative to 1 mol of organosilane. 0.8 to 2 mol of water is added to 1 mol of silane to carry out hydrolysis / condensation reaction, and (a) to
A method in which (e) fine particles are added and dispersed after forming a composition comprising the component (d). 1.2 to 3 mol of water and diorganosilane to 1 mol of organosilane in a solution comprising organosilane which constitutes component (a), diorganosilane which constitutes component (b), and (e) fine particles. Hydrolysis / condensation is carried out by adding 0.8 to 2 mol of water to 1 mol, then (c) silyl group-containing vinyl resin and (d) metal chelate compound are added and mixed, and further condensation reaction is carried out. Do (a)-(d)
A method in which a component (e) is added and dispersed after forming a composition comprising the components.

In the preparation of these compositions, as a device for uniformly mixing and dispersing each component and other thickeners, etc., which are added as necessary, a usual stirring blade such as a paddle or anchor type is used. In addition to the reaction device, a biaxial or triaxial stirring container equipped with a high-speed rotating stirring blade, a homodisper, a paint conditioner, a ball mill and the like can be mentioned. For dispersion, usually, the mixture can be mixed and dispersed at a temperature of 25 ° C. to a temperature not higher than the boiling point of the solvent in the composition for 5 minutes to 24 hours. The coating composition thus obtained is preferably purified by a filtration operation in order to maintain the appearance of the coated film and the uniformity of the surface.

The composition used in the present invention has a total solid content of usually 10 to 60% by weight, preferably 20 to 40% by weight.
Used as being in weight percent. If it is less than 10% by weight, the uniformity of the coating film is poor, while if it exceeds 60% by weight,
The storage stability of the composition may be impaired. The viscosity of the composition of the present invention is usually 5 to 1,000 mPa ·
s, preferably 10 to 500 mPa · s, 5 mP
If it is less than a · s and exceeds 1,000 mPa · s, it becomes difficult to obtain a uniform coating film.

Next, examples of the base material applied to the hard coat film of the present invention include metals, ceramics, paper and plastics, preferably plastics, more preferably plastics films,
A sheet-like base material can be mentioned. Examples of plastics include polyester such as polymethylmethacrylate, polycarbonate, polyethylene terephthalate and polybutylene terephthalate, nylon 4,
6, polyamide such as nylon 6, and the like. Further, the composition of the present invention can be directly applied to these various base materials, but it is also possible to use a base material on which various primers having acrylic urethane, epoxy, acryl silicon or the like as a main component are previously applied.

The hard coat film of the present invention is produced by
If necessary, an organic solvent, a curing accelerator, a thickener, a composition containing the above-mentioned components (a) to (e) as a main component in the present invention,
After mixing with other additives and the like, a brush, spray, dipping, bar coater is applied to the surface of the substrate, preferably a plastic substrate, more preferably a plastic film or sheet, particularly preferably a polyethylene terephthalate film. It is performed by coating with various coating methods such as a roll coater and a flow coater. The coating film thickness is a dry film thickness and is usually about 0.5 to 50 μm, preferably 1 to 30 μm after one coating, and if it is less than 0.5 μm, a uniform coating film may not be obtained. If it exceeds 50 μm, the bending workability of the film may decrease. Further, a coating film having a dry film thickness of about 2 to 150 μm can be formed by coating 2 to 3 times.
The curing temperature is appropriately set according to the heat resistance of the substrate,
Usually, it is 25 to 250 ° C., preferably 50 to 150 ° C., and the curing time is usually 5 seconds to 12 hours, preferably 1
A cured coating film can be formed by heating and drying for 5 seconds to 30 minutes.

The hard coat film of the present invention is coated
In order to improve the production speed, the drying step can be performed in two or more steps, for example, at a temperature of 50 to 250 ° C for 5 seconds to 1 minute, and then at a temperature of 25 ° C to less than 200 ° C. It can be heated and dried for 5 seconds to 12 hours. The hard coat film of the present invention usually has a pencil hardness of H to 8H. When the hardness is less than H, the abrasion resistance as a hard coat film is poor, and when the hardness is more than 8H, the adhesion to the film base material during bending is poor. In addition, the transparency of the hard coat film of the present invention depends on the compounding ratio of the composition composed of the components (a) to (e) of the present invention, for example, the particle size and the amount of (e) fine particles,
It can be controlled in the range of transparent, translucent, and opaque.

The preferred embodiment of the present invention is as follows. A hard coat film in which the (a ′) organosilane constituting the composition is methyltrimethoxysilane and / or methyltriethoxysilane. A hard coat film in which the (b ') diorganosilane constituting the composition is dimethyldimethoxysilane and / or dimethyldiethoxysilane. The (c) silyl group-containing vinyl resin constituting the composition is represented by the following general formula: A hard coat film obtained by copolymerizing a radically polymerizable silane compound represented by the formula (wherein R ^{1 to} R ² and X are the same as above) with various vinyl compounds. The metal chelate compound (d) constituting the composition is tri-n-butoxy (ethylacetoacetate) zirconium, diisopropoxy-bis (acetylacetonate).
A hard coat film which is at least one compound selected from the group consisting of titanium, diisopropoxy (ethylacetoacetate) aluminum and tris (ethylacetoacetate) aluminum. A hard coat film in which the (e) fine particles constituting the composition are colloidal silica dispersed in an organic solvent. A hard coat film whose base material is a polyethylene terephthalate film.

[0050]

The present invention will be described in more detail with reference to the following examples, but the invention is not limited to the following examples. In the examples, parts and% are based on weight unless otherwise specified. In addition, various measurements in the examples are as follows.

The polystyrene-reduced weight average molecular weight and number average molecular weight were measured by the gel permeation chromatography (GPC) method under the following conditions. A sample was prepared by dissolving 1 g of organopolysiloxane in 100 cc of tetrahydrofuran using tetrahydrofuran as a solvent. The standard polystyrene used was Standard Polystyrene manufactured by Pressure Chemical Co., USA. In addition, the silyl group-containing vinyl resin was prepared by dissolving 0.1 g of 100 cc of tetrahydrofuran. Device: Waters USA, high-temperature high-performance gel permeation chromatogram (model 150-C ALC / GPC) column: Showa Denko KK, SHODEX A-80
M, length 50 cm Measurement temperature; 40 ° C Flow rate; 1 cc / min

Test Piece Preparation Conditions Evaluation As a base material, a polyester film; Lumirror, manufactured by Toray Industries, Inc. was used. The coating was performed using a wire bar coater so that the film thickness when dried was 10 μm.
Unless otherwise specified, the coated film was dried in a hot air circulation dryer at 100 ° C. for 10 minutes.

Appearance of coating film evaluation standard : Uniformity of the coating film was visually evaluated, and good ones were evaluated as ◯, and those in which aggregates were observed were evaluated as x. Transparency; judged visually. Bending adhesion: Using a bending tester manufactured by Yoshimitsu Seiki Co., Ltd., a bending test was performed using a mandrel having a diameter of 2 to 10 mmφ, and then a peeling test was performed using cellophane tape. The minimum mandrel diameter without tape peeling was used as the evaluation value. Hardness: The pencil hardness test according to JIS K5400 was evaluated by the presence or absence of scratches. Scratch resistance: Scratch test was performed with a nail under a load of 3 kg. ○: No peeling of the surface ○, × scratches on the surface
It was determined. Stain resistance; draw a line on the coating with oil-based black magic ink,
After being dried at room temperature for 1 day, methanol was wiped off with a moistened gauze, and those whose appearance was recovered were evaluated as ◯, and those which were not recovered were evaluated as x.

Reference Example 1 (Preparation of vinyl resin containing silyl group) 90 parts of methyl methacrylate, 40 parts of n-butyl acrylate, 20 parts of γ-methacryloxypropyltrimethoxysilane were placed in a reactor equipped with a reflux condenser and a stirrer. Parts and 130 parts of xylene are added and mixed, and then stirred at 80 ° C.
Azobisisovaleronitrile 4 was added to this mixture after heating to
Part dissolved in 10 parts xylene was added dropwise over 30 minutes, and the mixture was further reacted at 80 ° C. for 5 hours to give a solid content concentration of 50.
% Silyl group-containing vinyl resin solution (a) was obtained. The polystyrene-reduced number average molecular weight of this silyl group-containing vinyl resin by gel permeation chromatography was 12,000, and it was estimated that each polymer molecule contained an average of 6 silyl groups.

Reference Example 2 (Preparation of Organopolysiloxane) In a reactor equipped with a reflux condenser and a stirrer, 100 parts of (a ') methyltrimethoxysilane, 30 parts of (b') dimethyldimethoxysilane and ion-exchanged water. 25 parts, 0.01 part of 0.1N hydrochloric acid water was added and mixed, and then 6 with stirring.
Warm up to 0 ° C and react at the same temperature for 3 hours to obtain a solid content of 4
A 4% organopolysiloxane solution (B) was obtained. The weight average molecular weight of this organopolysiloxane is 1,50
It was 0.

Reference Example 3 (Preparation of Example Compositions a to c) In a reactor equipped with a stirrer and a reflux condenser, 100 parts of (a ') methyltrimethoxysilane and 50 parts of (b') dimethyldimethoxysilane, (C) 50 parts of Kaneka Zemlac [Kanebuchi Chemical Industry Co., Ltd., solid content 50%], (d) diisopropoxyaluminum ethyl acetoacetate 20
Parts (0.07 molar equivalent) and 40 parts of i-propanol were added and mixed, 30 parts of ion-exchanged water was added, and the mixture was reacted at 60 ° C. for 4 hours and then cooled to room temperature, and the composition (c) was used.
I got Compositions (a) to (c) used in the examples were obtained by adding and dispersing various (e) fine particles in the composition shown in Table 1 to the composition (c). The dispersion conditions are as follows: in the case of Example composition c in which the fine particles are in the form of powder, the dispersion is treated with a homodisper at 2,000 rpm for 30 minutes, and otherwise with an anchor type stirring blade at 80 times / min. A dispersion was prepared by stirring for a minute.

Reference Example 4 (Preparation of Example Compositions d to f) In a reactor equipped with a stirrer and a reflux condenser, 155 parts of the organopolysiloxane solution (ii) obtained in Reference Example 2 and Reference Example 1 Silyl group-containing vinyl resin solution obtained in (a)
45 parts, (d) 8 parts (0.029 molar equivalent) of diisopropoxyaluminum ethylacetoacetate and 34 parts of i-propanol were added and mixed, and the mixture was reacted at 50 ° C. for 2 hours, and then 20 parts of acetylacetone (0 .2 molar equivalent) was added and the mixture was cooled to room temperature to obtain a composition (d) having a solid content concentration of 35%. For this composition (d), Table 1
Example compositions d to f were obtained by adding and dispersing various kinds of (e) fine particles in the composition shown in FIG. The dispersion conditions were the same as those for the above compositions a to c.

Reference Example 5 (Preparation of Example Compositions j to l) To the composition (d) obtained in Reference Example 4, 1 part of ethyl cellulose was further added, and the rotation was 80 rpm with an anchor type stirring blade. A uniform solution was obtained by stirring at 60 ° C. for 30 minutes under the conditions described above, and 338 parts of methanol silica sol was added to this over 5 minutes, and then stirred at the same temperature for 30 minutes to prepare a composition j. By the same operation, various fine particles having the composition shown in Table 2 were added and dispersed to obtain Example compositions j to l.

Reference Example 6 (Preparation of Comparative Compositions g to i) The silyl group-containing vinyl resin solution (a) obtained in Reference Example 1 and / or the organopolysiloxane solution obtained in Reference Example 2 ( In b), various fine particles and the like were added and dispersed under the compounding conditions shown in Table 1 to obtain compositions g to i of Comparative Examples. The dispersion treatment was carried out according to the composition a of the above example.
I went the same way.

Reference Example 7 (Preparation of Comparative Compositions m to o) The silyl group-containing vinyl resin solution (a) obtained in Reference Example 1 and / or the organopolysiloxane solution obtained in Reference Example 2 ( In b), various fine particles and the like were added and dispersed under the compounding conditions shown in Table 2 to obtain compositions m to o of comparative examples. The dispersion treatment was carried out according to the composition a of the above example.
I went the same way.

Examples 1 to 6 and Comparative Examples 1 to 3 2% of dibutyl tin laurate was added as a curing accelerator to the composition formulations shown in Table 1 and coated to obtain test pieces. The evaluation results of this test piece are shown in Table 3.

Examples 7 to 12 and Comparative Examples 4 to 6 For the composition formulations shown in Table 1, di-n was used as a curing accelerator.
A coating solution prepared by adding 5% of butoxy-bis (ethylacetoacetate) zirconium was applied onto the polyester film primer-coated with an epoxy resin [Eikaka Shell Co., Ltd., Epicoat 1003] to a thickness of 2 μm. After drying at 80 ℃ for 30 seconds, 150 more
A test piece was prepared by heating at 0 ° C for 1 hour. The results of these evaluations are shown in Table 4.

Examples 13 to 15 and Comparative Examples 7 to 9 Prepared by adding 5% of di-n-butoxy-bis (ethylacetoacetate) zirconium as a curing accelerator to the thickener composition shown in Table 2. Epoxy resin manufactured by Yuka Shell Co., Ltd., Epicoat 100
3] was applied onto the above polyester film having a thickness of 2 μm and coated with a primer, dried at 80 ° C. for 30 seconds, and further heated at 150 ° C. for 1 hour to prepare a test piece. The results of these evaluations are shown in Table 5.

In Tables 1 and 2, * 1 to 4 are as follows. * 1) Fine particles a; methanol-dispersed colloidal silica [manufactured by Nissan Kagaku Co., Ltd., methanol silica sol, solid content 30]
%, Medium; methanol, particle diameter = 15 μm] * 2) Fine particles b; isopropanol-dispersed colloidal silica [manufactured by Nissan Kagaku KK, IPA-ST, solid content 30%,
Medium; isopropanol, particle size = 15 μm] * 3) Fine particles c; spherical silica powder [Tatsumori Co., Ltd., Admafine SO-C2, particle size = 0.8 μm] * 4) Thickener d; ethyl cellulose [Shin-Etsu Chemical Industry Co., Ltd.]

[0065]

[Table 1]

[0066]

[Table 2]

[0067]

[Table 3]

[0068]

[Table 4]

[0069]

[Table 5]

[0070]

EFFECTS OF THE INVENTION According to the present invention, there is provided a hard coat film based on plastic or the like, which has excellent appearance, high hardness, scratch resistance, bending adhesion, stain resistance, and can control a wide range of transparency. can get. The hard coat film of the present invention can be used for an abrasion resistant film, an anti-slip coat, a polishing film, an anti-glare coat film, a wallpaper for building interiors, etc. by taking advantage of the above properties.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location C09D 183/07

Claims (1)

[Claims] 1. (a) General formula R ¹ Si (OR ² ) ₃ (wherein R ¹ is an organic group having 1 to 8 carbon atoms, R ² is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a carbon atom). The hydrolyzate of organosilane represented by the formula 1 to 4) and / or its partial condensate is expressed in 100 parts by weight in terms of the organosilane based on (b) the general formula R ¹ ₂ Si (O
R ² ) ₂ (in the formula, R ¹ and R ² are the same as described above), the hydrolyzate of diorganosilane and / or its partial condensate are 0 to 150 parts by weight in terms of diorganosilane, (c ) 2 to 300 parts by weight of a silyl group-containing vinyl resin having at least one silyl group having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group at the terminal or side chain in one molecule of the polymer, (d) general Formula Zr (O
R ³ ) _p (R ⁴ COCHCOR ⁵ ) _4-p , Ti (O
R ³ ) _q (R ⁴ COCHCOR ⁵ ) _4-q and Al (O
R ³ ) _r (R ⁴ COCHCOR ⁵ ) _3-r (In the formula, R ³ and R ⁴ are the same or different, and are an alkyl group having 1 to 6 carbon atoms, and R ⁵ is an alkyl group having 1 to ⁵ carbon atoms or a carbon number. 1 to
0.01 to 5 at least one metal chelate compound selected from the group of compounds represented by 16 alkoxy groups, p and q are integers of 0 to 3, and r is an integer of 0 to 2).
Based on a composition containing 0 parts by weight, and (e) fine particles having a particle size of 5 nm to 100 μm in an amount of 5 to 200 parts by weight based on 100 parts by weight (solid content) of the total amount of the components (a) to (d), Hard coat film made by coating material.